Detergent composition comprising mid-chain branched surfactants

ABSTRACT

The present invention relates to detergent compositions comprising anionic mid-branched surfactant compounds and additional anionic sulfate and sulfonate surfactants. The compositions are particularly useful as solid laundry detergent compositions.

TECHNICAL FIELD

The present invention relates to detergent compositions comprising anionic mid-branched surfactant compounds and additional anionic sulfate and sulfonate surfactants. The compositions are particularly useful as solid laundry detergent compositions.

BACKGROUND TO THE INVENTION

Recently, a certain new type of anionic mid-chain branched surfactants has been developed. These surfactants are described in unpublished co-pending applications U.S. Ser. No. 97/06485, U.S. Ser. No. 97/06474, U.S. Ser. No. 97/06339, U.S. Ser. No. 97/06476 and U.S. Ser. No. 97/06338.

It has been determined that these mid-chain branched surfactants are excellent surfactants, in particular for use in laundry products, especially under cool or cold water washing conditions even as low as 20° C.-5° C. It has also been found that combination of two or more of these mid-chain branched surfactants can provide a surfactant mixture that is even higher in surfactancy and has better low temperature water solubility.

Surprisingly, it has now been found that detergent compositions comprising these mid-chain branched surfactants and an additional sulphate and sulphonate surfactant, present in specific ratios, has an improved cleaning performance, in particular of greasy stains and soils. It has been found that lower levels of the additional anionic sulfate and sulfonate surfactants, which are traditionally known and used in detergent formulations, can still have excellent cleaning performance when combined with the mid-chain branched anionic surfactants. An additional benefit of such a combination can be that it allows the reduction of the levels of (or even the elimination of) other surfactants which are traditionally employed in detergents, such as nonionic surfactants, whilst still achieving an excellent cleaning performance. Thus, the inclusion of the specific mid-chain branched surfactants in detergent compositions comprising anionic sulfate and sulfonate surfactants, allows an overall reduction of the levels and types of surfactants needed, to obtain excellent cleaning performance. Another additional benefit is that hereby the formulation costs can be reduced and the ease of formulation can be improved.

All documents cited are hereby incorporate herein by reference.

SUMMARY OF THE INVENTION

The invention relates to detergent compositions, preferably being solid laundry detergent compositions, comprising

a) at least 0.5%, preferably at least 5%, more preferably at least 10% by weight of the composition a surfactant system, comprising one or more longer alkyl chain, mid-chain branched surfactant compounds of the formula:

A^(b)—X—B

 wherein:

(I) A^(b) is a hydrophobic mid-chain branched alkyl moiety, having in total 9 to 22 carbons in the moiety, preferably from 12 to about 18, having: (1) a longest linear carbon chain attached to the —X—B moiety in the range of from 8 to 21 carbon atoms; (2) one or more C₁-C₃ alkyl moieties branching from this longest linear carbon chain; (3) at least one of the branching alkyl moieties is attached directly to a carbon of the longest linear carbon chain at a position within the range of the position 2 carbon, counting from position 1 carbon (#1) which is attached to the —X—B moiety, to the position of the terminal carbon minus 2 carbons, (the (ω-2) carbon); and (4) when more than one of these compounds is present, the average total number of carbon atoms in the A^(b)—X moieties in the above formula is within the range of greater than 14.5 to about 18, preferably from about 15 to about 17;

(II) B is a hydrophobic moiety selected from sulfates, sulfonates, amine oxides, polyoxyalkylene, preferably polyoxyethylene and polyoxypropylene, alkoxylated sulfates, polyhydroxy moieties, phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccaminates, polyalkoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulfates, polyglycerol ethers, polyglycerol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonioalkanesulfonates, amidopropyl betaines, alkylated quats, alkyated/polyhydroxyalkylated quats, alkylated quats, alkylated/polyhydroxylated oxypropyl quats, imidazolines, 2-yl-succinates, sulfonated alkyl esters, and sulfonated fatty acids; and

(III) X is selected from —CH₂— and —C(O—; and

b) at least about 0.5%, preferably at least about 5%, more preferably at least about 10% by weight of the composition of an additional sulfate surfactant; and

c) at least about 0.5%, preferably at least about 5%, more preferably at least about 10% by weight of the composition of an additional sulfonate surfactant,

whereby the ratio of the surfactant system a) to the surfactant b) is from 20:1 to 1:20 and the ratio of surfactant system a) to the surfactant c) is from 20:1 to 1:10.

Preferably, the surfactant system a) comprises mid-chain branched primary alkyl sulfate or sulfonate surfactants.

DETAILED DESCRIPTION OF THE INVENTION Mid-Chain Branched Surfactant Compounds-Containing Surfactant System

The detergent compositions of the invention comprise at least 0.5%, preferably at least 5%, more preferably at least 10% by weight of the composition of a surfactant system, comprising longer alkyl chain, mid-chain branched surfactant compounds, selected from the group consisting of surfactant compounds having the formula as defined above.

Preferred surfactant systems herein comprise longer alkyl chain, mid-chain branched surfactant compounds of the above formula wherein the A^(b) moiety is a branched primary alkyl moiety having the formula:

wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula (including the R, R¹, and R² branching) is from 13 to 19; R, R¹, and R² are each independently selected from hydrogen and C₁-C₃ alkyl (preferably methyl), provided R, R¹, and R² are not all hydrogen and, when z is 0, at least R or R¹ is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer from 0 to 13; and w+x+y+z is from 7 to 13.

In general, for the mid-chain branched surfactant compounds of the surfactant system, certain points of branching (e.g., the location along the chain of the R, R¹, and/or R² moieties in the above formula) are preferred over other points of branching along the backbone of the surfactant. The formula below illustrates the mid-chain branching range (i.e., where points of branching occur), preferred mid-chain branching range, and more preferred mid-chain branching range for mono-methyl branched alkyl A^(b) moieties useful according to the present invention.

It should be noted that for the mono-methyl substituted surfactants these ranges exclude the two terminal carbon atoms of the chain and the carbon atom immediately adjacent to the —X—B group.

The formula below illustrates the mid-chain branching range, preferred mid-chain branching range, and more preferred mid-chain branching range for di-methyl substituted alkyl A^(b) moieties useful according to the present invention.

Preferred are surfactant compounds wherein in the above formula the A^(b) moiety does not have any quaternary substituted carbon atoms (i.e., 4 carbon atoms directly attached to one carbon atom).

The most preferred mid-chain branched surfactants compounds for use in the detergent compositions herein are mid-chain branched primary alkyl sulfonate and, even more preferably, sulfate surfactants.

Preferred mid-chain branched primary alkyl sulfate surfactants are of the formula

These surfactants have a linear primary alkyl sulfate chain backbone (i.e., the longest linear carbon chain which includes the sulfated carbon atom) which preferably comprises from 12 to 19 carbon atoms and their branched primary alkyl moieties comprise preferably a total of at least 14 and preferably no more than 20, carbon atoms. In the surfactant system comprising more than one of these sulfate surfactants, the average total number of carbon atoms for the branched primary alkyl moieties is preferably within the range of from greater than 14.5 to about 17.5. Thus, the surfactant system preferably comprises at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl moiety is within the range of greater than 14.5 to about 17.5.

R, R¹, and R² are each independently selected from hydrogen and C₁-C₃ alkyl group (preferably hydrogen or C₁-C₂ alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R¹, and R² are not all hydrogen. Further, when z is 1, at least R or R¹ is not hydrogen.

M is hydrogen or a salt forming cation depending upon the method of synthesis. Examples of salt forming cations are lithium, sodium, potassium, calcium, magnesium, quaternary alkyl amines having the formula

wherein R³, R⁴, R⁵ and R⁶ are independently hydrogen, C₁-C₂₂ alkylene, C₄-C₂₂ branched alkylene, C₁-C₆ alkanol, C₁-C₂₂ alkenylene, C₄-C₂₂ branched alkenylene, and mixtures thereof. Preferred cations are ammonium (R³, R⁴, R⁵ and R⁶ equal hydrogen), sodium, potassium, mono-, di-, and trialkanol ammonium, and mixtures thereof. The monoalkanol ammonium compounds of the present invention have R³ equal to C₁-C₆ alkanol, R⁴, R⁵ and R⁶ equal to hydrogen; dialkanol ammonium compounds of the present invention have R³ and R⁴ equal to C₁-C₆ alkanol, R⁵ and R⁶ equal to hydrogen; trialkanol ammonium compounds of the present invention have R³, R⁴ and R⁵ equal to C₁-C₆ alkanol, R⁶ equal to hydrogen. Preferred alkanol ammonium salts of the present invention are the mono-, di- and tri- quaternary ammonium compounds having the formulas:

H₃N⁺CH₂CH₂OH, H₂N⁺(CH₂CH₂OH)₂, HN⁺(CH₂CH₂OH)₃.

Preferred M is sodium, potassium and the C₂ alkanol ammonium salts listed above; most preferred is sodium.

Further regarding the above formula, w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1; and w+x+y+z is an integer from 8 to 14.

Another preferred surfactant system of the present invention have one or more branched primary alkyl sulfates having the formula

wherein the total number of carbon atoms, including branching, is from 15 to 18, and when more than one of these sulfates is present, the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14.5 to about 17.5; R¹ and R² are each independently hydrogen or C₁-C₃ alkyl; M is a water soluble cation; x is from 0 to 11; y is from 0 to 11; z is at least 2; and x+y+z is from 9to 13; provided R¹ and R² are not both hydrogen.

Preferably, the surfactant system comprises at least 20% by weight of the system, more preferably at least 60% by weight, even more preferably at least 90% by weight of the system, of mid-chain branched primary alkyl sulfates, preferably having R¹ and R² independently hydrogen or methyl, provided R¹ and R² are not both hydrogen; x+y is equal to 8, 9, or 10 and z is at least 2, whereby the average total number of carbon atoms in these sulfate surfactants is preferably from 14 to 18, more preferably from 15 to 17, even more preferably from 16 to 17.

Furthermore, preferred surfactant systems are those, which comprise at least about 20%, more preferably at least 60%, even more preferably at least 905 by weight of the system, of one or more mid-chain branched alkyl sulfates having the formula:

or mixtures thereof; wherein M represents one or more cations; a, b, d, and e are integers, a+b is from 10 to 16, d+e is from 8 to 14 and wherein further when a+b=10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a+b=11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a+b=12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a+b=13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a+b=14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a+b=15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a+b=16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d+e=8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d+e=9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d+e=10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d+e=11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d+e=12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d+e=13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d+e=14, d is an integer from 2 to 13 and e is an integer from 1 to 12; whereby, when more than one of these sulfate surfactants is present in the surfactant system, the average total number of carbon atoms in the branched primary alkyl moieties having the above formulas is within the range of greater than 14.5 to about 17.5.

Preferred mono-methyl branched primary alkyl sulfates are selected from the group consisting of: 3-methyl pentadecanol sulfate, 4-methyl pentadecanol sulfate, 5-methyl pentadecanol sulfate, 6methyl pentadecanol sulfate, 7-methyl pentadecanol sulfate, 8-methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl pentadecanol sulfate, 11-methyl pentadecanol sulfate, 12-methyl pentadecanol sulfate, 13-methyl pentadecanol sulfate, 3-methyl hexadecanol sulfate, 4-methyl hexadecanol sulfate, 5-methyl hexadecanol sulfate, 6-methyl hexadecanol sulfate, 7-methyl hexadecanol sulfate, 8-methyl hexadecanol sulfate, 9-methylhexadecanol sulfate, 10-methyl hexadecanol sulfate, 11-methyl hexadecanol sulfate, 12-methyl hexadecanol sulfate, 13-methyl hexadecanol sulfate, 14-methyl hexadecanol sulfate, and mixtures thereof.

Preferred di-methyl branched primary alkyl sulfates are selected from the group consisting of: 2,3-methyl tetradecanol sulfate, 2,4-methyl tetradecanol sulfate, 2,5-methyl tetradecanol sulfate, 2,6-methyl tetradecanol sulfate, 2,7-methyl tetradecanol sulfate, 2,8-methyl tetradecanol sulfate, 2,9-methyl tetradecanol sulfate, 2,10-methyl tetradecanol sulfate, 2,11-methyl tetradecanol sulfate, 2,12-methyl tetradecanol sulfate, 2,3-methyl pentadecanol sulfate, 2,4-methyl pentadecanol sulfate, 2,5-methyl pentadecanol sulfate, 2,6-methyl pentadecanol sulfate, 2,7-methyl pentadecanol sulfate, 2,8-methyl pentadecanol sulfate, 2,9-methyl pentadecanol sulfate, 2,10-methyl pentadecanol sulfate, 2,11-methyl pentadecanol sulfate, 2,12-methyl pentadecanol sulfate, 2,13-methyl pentadecanol sulfate, and mixtures thereof.

The following branched primary alkyl sulfates comprising 16 carbon atoms and having one branching unit are examples of preferred branched surfactants useful in the present invention compositions:

5-methylpentadecylsulfate having the formula:

6-methylpentadecylsulfate having the formula

7-methylpentadecylsulfate having the formula

8-methylpentadecylsulfate having the formula

9-methylpentadecylsulfate having the formula

10-methylpentadecylsulfate having the formula

wherein M is preferably sodium.

The following branched primary alkyl sulfates comprising 17 carbon atoms and having two branching units are examples of preferred branched surfactants according to the present invention:

2,5-dimethylpentadecylsulfate having the formula:

2,6-dimethylpentadecylsulfate having the formula

2,7-dimethylpentadecylsulfate having the formula

2,8-dimethylpentadecylsulfate having the formula

2,9-dimethylpentadecylsulfate having the formula

2,10-dimethylpentadecylsulfate having the formula

wherein M is preferably sodium.

Additional Sulfonate Surfactant

The detergent compositions of the present invention comprise an additional sulfonate surfactant. This surfactant can be any sulfonate surfactant known in the art, not being a sufonate surfactant as defined in the description of the mid-chain branched surfactant system above. Preferred sulfonate surfactants are described herein. The ratio of the surfactant system to the additional sulfonate surfactant is preferably from 10:1 to 1:5, more preferably from 5:1 to 1:1, even more preferably from 4:1 to 2:1.

Preferred additional sulfonate surfactants for the detergent compositions of the present invention are the salts of C₅-C₂₀ linear alkylbenzene sulfonates, C₆-C₂₂ primary or secondary alkane sulfonates, C₆-C₂₄ olefin sulphonates, sulphonated polycarboxylic acids, and any mixtures thereof. Highly preferred is a C11-C16 linear alkylbenzene sulphonate. Preferred salts are sodium and potassium salts.

Alkyl ester sulphonated surfactant are other preferred additional sulfonate surfactants for the detergent compositions of the invention. Preferred are those of the formula

R¹—CH(SO₃M)—(A)_(x)—C(O)—OR²

wherein R¹ is a C₆-C₂₂ hydrocarbyl, R² is a C₁-C₆ alkyl, A is a C₆-C₂₂ alkylene, alkenylene, x is 0 or 1, and M is a cation. Preferred is an α-methyl ester sulfonate surfactant. The counterion M is preferably sodium, potassium or ammonium.

The alkyl ester sulphonated surfactant is preferably a α-sulpho alkyl ester of the formula above, whereby thus x is 0. Preferably, R¹ is an alkyl or alkenyl group of from 10 to 22, preferably 16 C atoms and x is preferably 0. R² is preferably ethyl or more preferably methyl.

It can be preferred that the R1 of the ester is derived from unsaturated fatty acids, with preferably 1, 2 or 3 double bonds. It can also be preferred that R¹ of the ester is derived from a natural occurring fatty acid, preferably palmic acid or stearic acid or mixtures thereof.

Additional Sulfate Surfactant

The detergent compositions of the present invention comprise an additional sulfate surfactant. This surfactant can be any sulfate surfactant known in the art, not being a sufate surfactant as defined in the description of the mid-chain branched surfactant system above. Preferred sulfate surfactants are described herein.

The ratio of the surfactant system to the additional sulfate surfactant is preferably from 10:1 to 1:10, more preferably from 4:1 to 1:2, even more preferably from 2:1 to 1:2.

Anionic (mono) sulfate surfactants are preferred additional sulfate surfactants for use in the detergent compositions of the present invention. These include the linear and branched, other than mid-chain branched surfactants of the invention, primary and secondary saturated and unsaturated alkyl sulfates, alkyl ethoxysulfates having an average ethoxylation number of from 0.5 to 15, preferably from 3 to 7, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C₅-C₁₇ acyl-N-(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides. or glucosides

Primary alkyl mono-sulfate surfactants are preferably selected from the linear and branched primary C₁₀-C₁₈ alkyl sulfates, more preferably the C₁₂-C₁₅ chain alkyl sulfates and the C₁₂-C₁₅ linear chain alkyl sulfates.

Preferred secondary alkyl mono-sulfate surfactant are of the formula

R³—CH(SO₄M)—R⁴

wherein R³ is a C₈-C₂₀hydrocycarbyl, R⁴ is a hydrocycarbyl and M is a cation.

Alkyl ethoxy mono-sulfate surfactants are preferably selected from the group consisting of the C₁₀-C₁₈ alkyl sulphates which have been ethoxylated with from 0.5 to 15 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C₁₁-C₁₈, most preferably C₁₁-C₁₅ alkyl sulfate which has been ethoxylated with from 3 to 9, preferably from 3 to 7, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Preferred salts are sodium and potassium salts.

Additional Sulfate or Sulfonate Surfatcant: Dianionic Surfactants

The additional sulfate surfactant or the additional sulfonate surfactant of the detergent compositions of the invention can also comprise dianionic surfactants, which comprise two anionic groups, each of which can be independently a sulfate or sufonate group, but which can also be a sulfate and a sulfonate group. Therefor, these dianionc surfactants are to be considered either additional sulfate or additional sulfonate surfactants for use in the detegergent compositions of the invention, depending on their anionic groups.

The dianionic surfactants, for use in the detergent compositions of the present invention are of the formula:

where R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C₁ to C₂₈, preferably C₃ to C₂₄, most preferably C₈ to C₂₀, or hydrogen; A and B are independently selected from alkylene, alkenylene, (poly) alkoxylene, hydroxyalkylene, arylalkylene or amido alkylene groups of chain length C₁ to C₂₈ preferably C₁ to C₅, most preferably C₁ or C₂, or a covalent bond, and preferably A and B in total contain at least 2 atoms; A, B, and R in total contain from 4 to about 31 carbon atoms; X and Y are anionic groups selected from the group comprising carboxylate, and preferably sulfate and sulfonate, provided that al least one anionic group X or y is a sulfate or a sulfonate group, z is 0 or preferably 1; and M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali or alkaline earth metal ion.

The most preferred dianionic surfactant has the formula as above where R is an alkyl group of chain length from C₁₀ to C₁₈, A and B are independently C₁ or C₂, both X and Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.

Preferred dianionic surfactants herein include:

(a) 3 disulphate compounds, preferably 1,3 C7-C23 (i.e., the total number of carbons in the molecule) straight or branched chain alkyl or alkenyl disulphates, more preferably having the formula:

 wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C₄ to about C₂₀;

(b) 1,4 disulphate compounds, preferably 1,4 C8-C22 straight or branched chain alkyl or alkenyl disulphates, more preferably having the formula:

 wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C₄ to about C₁₈; preferred R are selected from octanyl, nonanyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and mixtures thereof; and

(c) 1,5 disulphate compounds, preferably 1,5 C9-C23 straight or branched chain alkyl or alkenyl disulphates, more preferably having the formula:

 wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C₄ to about C₁₈.

It can be preferred that the dianionic surfactants of the invention are alkoxylated dianionic surfactants.

The alkoxylated dianionic surfactants of the invention comprise a structural skeleton of at least five carbon atoms, to which two anionic substituent groups spaced at least three atoms apart are attached. At least one of said anionic substituent groups is an alkoxy-linked sulphate or sulphonate group. Said structural skeleton can for example comprise any of the groups consisting of alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine and amide groups. Preferred alkoxy moieties are ethoxy, propoxy, and combinations thereof.

The structural skeleton preferably comprises from 5 to 32, preferably 7 to 28, most preferably 12 to 24 atoms. Preferably the structural skeleton comprises only carbon-containing groups and more preferably comprises only hydrocarbyl groups. Most preferably the structural skeleton comprises only straight or branched chain alkyl groups.

The structural skeleton is preferably branched. Preferably at least 10% by weight of the structural skeleton is branched and the branches are preferably from 1 to 5, more preferably from 1 to 3, most preferably from 1 to 2 atoms in length (not including the sulphate or sulphonate group attached to the branching).

A preferred alkoxylated dianionic surfactant has the formula

where R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C₁ to C₂₈, preferably C₃ to C₂₄, most preferably C₈ to C₂₀, or hydrogen; A and B are independently selected from, optionally substituted, alkyl and alkenyl group of chain length C₁ to C₂₈, preferably C₁ to C₅, most preferably C₁ or C₂, or a covalent bond; EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein n and m are independently within the range of from about 0 to about 10, with at least m or n being at least 1; A and B in total contain at least 2 atoms; A, B, and R in total contain from 4 to about 31 carbon atoms; X and Y are anionic groups selected from the group consisting of sulphate and sulphonate, provided that at least one of X or Y is a sulfate group; and M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali or alkaline earth metal ion.

The most preferred alkoxylated dianionic surfactant has the formula as above where R is an alkyl group of chain length from C₁₀ to C₁₈, A and B are independently C₁ or C₂, n and m are both 1, both X and Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.

The alkoxylated dianionic cleaning agent is typically present at levels of incorporation of from about 0.1% to about 20%, preferably from about 0.3% to about 15%, most preferably from about 0.5% to about 10% by weight of the bleaching detergent composition.

Preferred alkoxylated dianionic surfactants herein include:

ethoxylated and/or propoxylated disulphate compounds, preferably C10-C24 straight or branched chain alkyl or alkenyl ethoxylated and/or propoxylated disulphates, more preferably having the formulae:

wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C6 to about C₁₈; EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups; and n and m are independently within the range of from about 0 to about 10 (preferably from about 0 to about 5), with at least m or n being 1.

Additional Detergent Components

The detergent compositions in accord with the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition or component, and the precise nature of the washing operation for which it is to be used.

The compositions of the invention preferably contain one or more additional detergent components selected from other surfactants, bleaches, bleach catalysts, alkalinity systems, builders, phosphate-containing builders, organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti-redeposition agents soil releasing agents, perfumes, brightners, photobleaching agents and additional corrosion inhibitors.

Other Surfactant

The detergent compositions in accord with the invention can contain one or more other surfactants selected from nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

A typical listing of nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. Further examples are given in “Surface Active Agents and Detergents” (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S. Pat. No. 4,259,217 issued to Murphy on Mar. 31, 1981.

When present in the detergent compositions of the invention, the nonionic surfactants are preferably present in low levels, preferably from 0.5% to 20%, more preferably from 1% to 15%, even more preferably from 1.5% to 8% by weight. The ratio of the nonionic surfactants, when present, to the surfactant system is preferably from 5:1 to 1:20, more preferably from 5:1 to 1:10, even more preferably from 1:1 to 1:10.

Alkoxylated Nonionic Surfactant

Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.

Nonionic Alkoxylated Alcohol Surfactant

The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms or more preferably 9 to 15 with from 3 to 12 moles of ethylene oxide per mole of alcohol.

Nonionic Polyhydroxy Fatty Acid Amide Surfactant

Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R²CONR¹Z wherein: R1 is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C₁ or C₂ alkyl, most preferably C₁ alkyl (i.e., methyl); and R₂ is a C₅-C₃₁ hydrocarbyl, preferably straight-chain C₅-C₁₉ alkyl or alkenyl, more preferably straight-chain C₉-C₁₇ alkyl or alkenyl, most preferably straight-chain C₁₁-C₁₇ alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.

Nonionic Fatty Acid Amide Surfactant

Suitable fatty acid amide surfactants include those having the formula: R⁶CON(R⁷)₂ wherein R⁶ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R⁷ is selected from the group consisting of hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, and —(C₂H₄O)_(x)H, where x is in the range of from 1 to 3.

Nonionic Alkylpolysaccharide Surfactant

Suitable alkylpolysaccharides for use herein are disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophobic group containing from 1.3 to 10 saccharide units.

Preferred alkylpolyglycosides have the formula:

R²O(C_(n)H_(2n)O)t(glycosyl)_(x)

wherein R² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

Amphoteric Surfactant

Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formula R³(OR⁴)_(x)N⁰(R⁵)₂ wherein R³ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R⁴ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R⁵ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are C₁₀-C₁₈ alkyl dimethylamine oxide, and C₁₀₋₁₈ acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(™) C2M Conc. manufactured by Miranol, Inc., Dayton, N.J.

Zwitterionic Surfactant

Zwitterionic surfactants can also be incorporated into the detergent in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R(R′)₂N⁺R²COO⁻ wherein R is a C₆-C₁₈ hydrocarbyl group, each R¹ is typically C₁-C₃ alkyl, and R² is a C₁-C₅ hydrocarbyl group. Preferred betaines are C₁₂₋₁₈ dimethyl-ammonio hexanoate and the C₁₀₋₁₈ acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Cationic Surfactants

Suitable cationic surfactants to be used in the detergent include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono C₆-C₁₆, preferably C₆-C₁₀ N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.

Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants.

The cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i.e. —COO—) linkage and at least one cationically charged group.

Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in U.S. Pat. Nos. 4,228,042, 4,239,660 and 4260529.

In one preferred aspect the ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain. Thus spacer groups having, for example, —O—O— (i.e. peroxide), —N—N—, and —N—O— linkages are excluded, whilst spacer groups having, for example —CH₂—O—CH₂— and —CH₂—NH—CH₂— linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.

Cationic Mono-Alkoxylated Amine Surfactants

The cationic mono-alkoxylated amine surfactant are preferably of the general formula I:

wherein R¹ is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R² and R³ are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R² and R³ are methyl groups; R⁴ is selected from hydrogen (preferred), methyl and ethyl; X⁻ is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8, with the proviso that if A is ethoxy and R₄ is hydrogen and p is 1, R₁ is not a C₁₂-C₁₄ alkyl group.

Preferably the ApR⁴ group in formula I has p=1 and is a hydroxyalkyl group, having no greater than 6 carbon atoms whereby the —OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred ApR⁴ groups are —CH₂CH₂OH, —CH₂CH₂CH₂OH, —CH₂CH(CH₃)OH and —CH(CH₃)CH₂OH, with —CH₂CH₂OH being particularly preferred. Preferred R¹ groups have have no greater than 10 carbon atoms, or even no greater than 8 or 9 carbon atoms. Preferred R¹ groups are linear alkyl groups. Linear R¹ groups having from 8 to 11 carbon atoms, or from 8 to 10 carbon atoms are preferred. Such a cationic surfactant which is highly preferred has a formula wherein R₁ is a C₈-C₁₀ alkyl group, p is 1, A is ethoxy and R₂ and R₃ are methyl groups.

Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula

wherein R¹ is C₁₀-C₁₈ hydrocarbyl and mixtures thereof, especially C₁₀-C₁₄ alkyl, preferably C₁₀ and C₁₂ alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.

As noted, compounds of the foregoing type include those wherein the ethoxy (CH₂CH₂O) units (EO) are replaced by butoxy, isopropoxy [CH(CH₃)CH₂O] and [CH₂CH(CH₃O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

The levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%, more preferably from 0.4% to 7%, most preferably from 0.5% to 3.0% by weight of the composition.

Cationic Bis-Alkoxylated Amine Surfactant

The cationic bis-alkoxylated amine surfactant preferably has the general formula II:

wherein R¹ is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R² is an alkyl group containing from one to three carbon atoms, preferably methyl; R³ and R⁴ can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X⁻ is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A′ can vary independently and are each selected from C₁-C₄ alkoxy, especially ethoxy, (i.e., —CH₂CH₂O—), propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.

Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula

wherein R¹ is C₁₀-C₁₈ hydrocarbyl and mixtures thereof, preferably C₁₀, C₁₂, C₁₄ alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in a preferred compound R¹ is derived from (coconut) C₁₂-C₁₄ alkyl fraction fatty acids, R² is methyl and ApR³ and A′qR⁴ are each monoethoxy.

Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:

wherein R¹ is C₁₀-C₁₈ hydrocarbyl, preferably C₁₀-C₁₄ alkyl, independently p is 1 to about 3 and q is 1 to about 3, R² is C₁-C₃ alkyl, preferably methyl, and X is an anion, especially chloride or bromide.

Other compounds of the foregoing type include those wherein the ethoxy (CH₂CH₂O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH₃)CH₂O] and [CH₂CH(CH₃O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

The levels of the cationic bis-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%, more preferably from 0.4% to 7%, most preferably from 0.5% to 3.0% by weight of the composition.

Optional Surfactants

Suitable optional soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors.

Other optional additional anionic surfactants are the carboxylate-based anionic surfactants known in the art and alkali metal sarcosinates of formula R—CON (R¹) CH₂COOM, wherein R is a C₅-C₁₇ linear or branched alkyl or alkenyl group, R¹ is a C₁-C₄ alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts

Water-Soluble Builder Compound

The detergent compositions in accord with the present invention preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.

The detergent compositions of the invention can comprise phosphate-containing builder material, preferably present at a level of from 0.015 to 50%, more preferably from 5% to 30%, more preferably from 8% to 25%, most preferably from 12% to 205 by weight of the composition. The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate. It can be preferred that the compositions are free form phosphate-containing builders

Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.

The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present a t a level of from 0.1% to 15%, more preferably from 0.5% to 8% by weight of the composition.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.

Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.

Partially Soluble or Insoluble Builder Compound

The detergent compositions in accord with the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.

Examples of largely water insoluble builders include the sodium aluminosilicates.

Suitable aluminosilicate zeolites have the unit cell formula Na_(z)[(AlO₂)_(z)(SiO₂)_(y)].xH₂O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:

Na₁₂[AlO₂)₁₂(SiO₂)₁₂].xH₂O

wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na₈₆ [(AlO₂)₈₆(SiO₂)₁₀₆].276H₂O.

Another preferred aluminosilicate zeolite is zeolite MAP builder. The zeolite MAP can be present at a level of from 1% to 80%, more preferably from 15% to 40% by weight of the compositions.

Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkai metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.

Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.

In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a d₅₀ value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.

The d₅₀ value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d₅₀ values are disclosed in EP 384070A.

Perhydrate Bleaches

An preferred additional components of the detergent composition is a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts. Perborate can be mono or tetra hydrated. Sodium percarbonate has the formula corresponding to 2Na₂CO₃.3H₂O₂, and is available commercially as a crystalline solid.

Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.

Organic Peroxyacid Bleaching System

A preferred feature of detergent composition is an organic peroxyacid bleaching system. In one preferred execution the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention. In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.

Peroxyacid Bleach Precursor

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as

where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is

Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Leaving Groups

The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.

Preferred L groups are selected from the group consisting of:

and mixtures thereof, wherein R¹ is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R³ is an alkyl chain containing from 1 to 8 carbon atoms, R⁴ is H or R³, and Y is H or a solubilizing group. Any of R¹, R³ and R⁴ may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmnonium groups.

The preferred solubilizing groups are —SO₃ ⁻M⁺, —CO₂ ⁻M⁺, —SO₄ ⁻M⁺, —N⁺(R³)₄X⁻ and O←N(R³)₃ and most preferably —SO₃ ⁻M⁺ and —CO₂ ⁻M⁺ wherein R³ is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Alkyl Percarboxylic Acid Bleach Precursors

Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N¹N¹ tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred. The TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.

Amide Substituted Plkyl Peroxyacid Precursors

Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:

wherein R¹ is an alkyl group with from 1 to 14 carbon atoms, R² is an alkylene group containing from 1 to 14 carbon atoms, and R⁵ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

Perbenzoic Acid Precursor

Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic Peroxyacid Precursors

Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammoniun or alkyl ammmonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.

The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter.

Cationic peroxyacid precursors are described in U.S. Pat. Nos. 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.

Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and U.S. patent application Ser. Nos. 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.

Benzoxazin Organic Peroxyacid Precursors

Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A482,807, particularly those having the formula:

wherein R₁ is H, alkyl, alkaryl, aryl, or arylalkyl.

Preformed Organic Peroxyacid

The organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1% to 15% by weight, more preferably from 1% to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:

wherein R¹ is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R² is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R⁵ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.

Bleach Catalyst

The bleach system can contain a transition metal containing bleach catalyst.

One suitable type of bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. No. 4,430,243.

Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. No. 5,246,621 and U.S. Pat. No. 5,244,594. Preferred examples of these catalysts include Mn^(IV) ₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(PF₆)₂, Mn^(III) ₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂—(ClO₄)₂, Mn^(IV) ₄(u-O)₆(1,4,7-triazacyclononane)₄—(ClO₄)₂, Mn^(III)Mn^(IV) ₄(u-O)₁(u-OAc)₂—(1,4,7-trimethyl-1,4,7-triazacyclononane)₂—(ClO₄)₃, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.

The bleach catalysts useful herein may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. Pat. No. 4,246,612 and U.S. Pat. No. 5,227,084. See also U.S. Pat. No. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH₃)₃—(PF₆).

Still another type of bleach catalyst, as disclosed in U.S. Pat. No. 5,114,606, is a water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C—OH groups.

Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.

U.S. Pat. No. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands are of the formula:

wherein R¹, R², R³, and R⁴ can each be selected from H, substituted alkyl and aryl groups such that each R¹—N═C—R² and R³—C═N—R⁴ form a five or six-membered ring. Said ring can further be substituted. B is a bridging group selected from O, S. CR⁵R⁶, NR⁷ and C═O, wherein R⁵, R⁶, and R⁷ can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2′-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and bispyridylamine complexes. Highly preferred catalysts include Co(2,2′-bispyridylamine)Cl₂, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)₂O₂ClO₄, Bis-(2,2′-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.

Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N₄Mn^(III)(u-O)₂Mn^(IV)N₄)⁺ and [Bipy₂Mn^(III)(u-O)₂Mn^(IV)bipy₂]—(ClO₄)₃.

Other bleach catalysts are described, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. Pat. No. 4,728,455 (manganese/multidentate ligand catalyst), U.S. Pat. No. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. Pat. No. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. Pat. No. 4,626,373 (manganese/ligand catalyst), U.S. Pat. No. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S. Pat. No. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. Pat. No. 4,728,455 (manganese gluconate catalysts).

The bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein. By “catalytically effective amount” is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrate. The test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some users elect to use very hot water; others use warm or even cold water in laundering operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in fully-formulated detergent and bleach compositions can be appropriately adjusted. As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 1 ppm to about 200 ppm of the catalyst species in the wash liquor. To illustrate this point further, on the order of 3 micromolar manganese catalyst is effective at 40° C., pH 10 under European conditions using perborate and a bleach precursor. An increase in concentration of 3-5 fold may be required under U.S. conditions to achieve the same results.

Enzyme

Another preferred ingredient useful in the detergent is one or more additional enzymes.

Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in U.S. Pat. Nos. 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.

Preferred amylases include, for example, α-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S. Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.

Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.

The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-02 18272.

Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Pat. No. 4,810,414, Huge-Jensen et al, issued Mar. 7, 1989.

Organic Polymeric Compound

Organic polymeric compounds are preferred additional components of the detergent compositions in accord with the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, not being an quaternised ethoxylated (poly) amine clay-soil removal/anti-redeposition agent in accord with the invention.

Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions.

Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.

The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.

Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.

Suds Suppressing System

The detergent compositions of the invention, when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition.

Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.

By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term “silicone” as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.

Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in U.S. Pat. No. 2,954,347, issued Sep. 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.

A preferred suds suppressing system comprises:

(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination

(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and

(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;

wherein said silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight;

(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1% to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544;

(c) an inert carrier fluid compound, most preferably comprising a C₁₆-C₁₈ ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;

A highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50° C. to 85° C., wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45° C. to 80° C.

Polymeric Dye Transfer Inhibiting Agents

The detergent compositions herein may also comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.

a) Polyamine N-Oxide Polymers

Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula:

wherein P is a polymerisable unit, and

R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N—O group can be attached or wherein the nitrogen of the N—O group is part of these groups.

The N—O group can be represented by the following general structures:

wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N—O group can be attached or wherein the nitrogen of the N—O group forms part of these groups. The N—O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N—O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N—O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N—O group is attached to the polymerisable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N—O functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.

The polyamine N-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000.

b) Copolymers of N-Vinylpyrrolidone and N-Vinylimidazole

Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.

c) Polyvinylpyrrolidone

The detergent compositions herein may also utilize polyvinylpyrrolidone (“PVP”) having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, N.Y. and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.

d) Polyvinyloxazolidone

The detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.

e) Polyvinylimidazole

The detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.

Optical Brightener

The detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophobic optical brighteners.

Hydrophobic optical brighteners useful herein include those having the structural formula:

wherein R₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R₂ is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4′,-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2′-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophobic optical brightener useful in the detergent compositions herein.

When in the above formula, R₁ is anilino, R₂ is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4′-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2′-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is a cation such as sodium, the brightener is 4,4′-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2′-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Polymeric Soil Release Agent

Known polymeric soil release agents, hereinafter “SRA”, can optionally be employed in the present detergent compositions. If utilized, SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the compositions.

Preferred SRA's typically have hydrophobic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophobic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.

Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.

Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. Pat. No. 4,968,451, Nov. 6, 1990 to J. J. Scheibel and E. P. Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S. Pat. No. 4,711,730, Dec. 8, 1987 to Gosselink et al., for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) (“PEG”). Other examples of SRA's include: the partly- and fully-anionic-end-capped oligomeric esters of U.S. Pat. No. 4,721,580, Jan. 26, 1988 to Gosselink, such as oligomers from ethylene glycol (“EG”), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. Pat. No. 4,702,857, Oct. 27, 1987 to Gosselink, for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. Pat. No. 4,877,896, Oct. 31, 1989 to Maldonado, Gosselink et al., the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.

SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. Pat. No. 3,959,230 to Hays, May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadur, Jul. 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C₁-C₄ alkyl celluloses and C₄ hydroxyalkyl celluloses, see U.S. Pat. No. 4,000,093, Dec. 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20° C. as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Additional classes of SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. Pat. No. 4,201,824, Violland et al. and U.S. Pat. No. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. Pat. No. 4,525,524 Tung et al. Other classes include: (III) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. Pat. No. 4,201,824, Violland et al.;

Other Optional Ingredients

Other optional ingredients suitable for inclusion in the compositions of the invention include colours and filler salts, with sodium sulfate being a preferred filler salt.

Highly preferred compositions preferably contain from about 2% to about 10% by weight of an organic citric acid, preferably citric acid. Also preferably in combination with a carbonate salt, minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides, dyes, perfumes, such as those described in U.S. Pat. No. 4,285,841 to Barrat et al., issued Aug. 25, 1981 (herein incorporated by reference), can be present in the compositions.

Form of the Compositions

The compositions in accordance with the invention can take a variety of physical forms including liquid but preferably solid forms such as tablet, flake, pastille and bar, and preferably granular forms.

The compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach, as mentioned above.

However, since preferred detergent compositions of the invention are solid, most liquid chlorine-based bleaching will not be suitable for these detergent compositions and only granular or powder chlorine-based bleaches will be suitable.

Alternatively, the detergent compositions can be formulated such that they are chlorine-based bleach-compatible, thus ensuring that a chlorine based bleach can be added to the detergent composition by the user at the beginning or during the washing process.

The chlorine-based bleachis such that a hypochlorite species is formed in aqueous solution. The hypochlorite ion is chemically represented by the formula OCI⁻.

Those bleaching agents which yield a hypochlorite species in aqueous solution include alkali metal and alkaline earth metal hypochlorites, hyposchlorite addition products, chloramines, chlorimines, chloramides, and chlorimides. Specific examples of compounds of this type include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dichloramine T, chloramine B and Dichloramine B. A preferred bleaching agent for use in the compositions of the instant invention is sodium hypochlorite, potassium hypochlorite, or a mixture thereof. A preferred chlorine-based bleach can be Triclosan (trade name).

Most of the above-described hypochlorite-yielding bleaching agents are available in solid or concentrated form and are dissolved in water during preparation of the compositions of the instant invention. Some of the above materials are available as aqueous solutions.

In general, granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.

The mid-chain branched surfactant system herein, preferably with the additional sulfate and/or sulfonate surfactants, is preferably present in granular compositions in the form of surfactant agglomerate particles, preferably not comprising the bleach precursors, which may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules. The most preferred way to process the particles is by agglomerating powders (e.g. aluminosilicate, carbonate) with high active surfactant pastes and to control the particle size of the resultant agglomerates within specified limits. Such a process involves mixing an effective amount of powder with a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderbom 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used, such as a Lodige CB (Trade Name).

A high active surfactant paste comprising from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of the surfactants, including the mid-chain branched surfactants, is typically used. The paste may be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the anionic surfactants used. An operating temperature of the paste of 50° C. to 80° C. is typical.

The mean particle size of the components of granular compositions in accordance with the invention, should preferably be such that no more that 25% of the particles are greater than 1.8 mm in diameter and not more than 25% of the particles are less than 0.25 mm in diameter. Preferably the mean particle size is such that from 10% to 50% of the particles has a particle size of from 0.2 mm to 0.7 mm in diameter.

The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of sieves, preferably Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.

The bulk density of granular detergent compositions in accordance with the present invention typically have a bulk density of at least 200 g/liter, more preferably from 300 g/liter to 1400 g/liter, more preferably from 330g/liter to 1200 gr/liter, most preferably from 380 g/liter to 850 g/ liter. Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.

To carry out a measurement, the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup. The filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/liter. Replicate measurements are made as required.

Laundry Washing Method

Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from 10 g to 300 g of product dissolved or dispersed in a wash solution of volume from 5 to 65 liters, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.

In a preferred use aspect the detergent composition is formulated such that it is suitable for hand washing.

In another preferred aspect the detergent composition is a pre-treatment or soaking composition, to be used to pre-treat or soak soiled and stained fabrics.

Abbreviations used in Examples

In the detergent compositions, the abbreviated component identifications have the following meanings:

LAS Sodium linear C₁₂ alkyl benzene sulfonate TAS Sodium tallow alkyl sulfate C45AS Sodium C₁₄—C₁₅ linear alkyl sulfate MES α-sulpho methylester of C₁₈ fatty acid CxyEzS Sodium C_(1x)—C_(1y) branched alkyl sulfate condensed with z moles of ethylene oxide MBAS_(x,y) Sodium mid-chain branched alkyl sulfate having an average of x carbon atoms, whereof an average of y carbons comprised in (a) branching unit(s) C₄₈ SAS Sodium C₁₄—C₁₈ secondary alcohol sulfate SADExS Sodium C₁₄—C₂₂ alkyl disulfate of formula 2-(R). C₄ H₇—1,4-(SO₄—)₂ where R = C₁₀OC₁₈, condensed with z moles of ethylene oxide C45E7 A C₁₄₋₁₅ predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide CxyEz A C_(1x-1y) branched primary alcohol condensed with an average of z moles of ethylene oxide QAS I R₂.N⁺(CH₃)₂(C₂H₄OH) with R₂ = 50%-60% C₉; 40%-50% C₁₁ QAS II R₁.N⁺(CH₃)(C₂H₄OH)₂ with R₁ = C₁₂—C₁₄ Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils. TFAA C₁₆—C₁₈ alkyl N-methyl glucamide TPKFA C12-C14 topped whole cut fatty acids STPP Anhydrous sodium tripolyphosphate Zeolite A Hydrated Sodium Aluminosilicate of formula Na₁₂(A10₂SiO₂)₁₂.27H₂O having a primary particle size in the range from 0.1 to 10 micrometers NaSKS-6 Crystalline layered silicate of formula δ-Na₂Si₂O₅ Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200 μm and 900 μm Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 μm and 1200 μm Silicate Amorphous Sodium Silicate (SiO₂:Na₂O; 2.0 ratio) Sodium sulfate Anhydrous sodium sulfate Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425 μm and q 850 μm MA/AA Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000 CMC Sodium carboxymethyl cellulose Protease Proteolytic enzyme of activity 4 KNPU/g sold by NOVO Industries A/S under the tradename Savinase Alcalase Proteolytic enzyme of activity 3 AU/g sold by NOVO Industries A/S Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tradename Carezyme Amylase Amylolytic enzyme of activity 60 KNU/g sold by NOVO Industries A/S under the tradename Termamyl 60 T Lipase Lipolytic enzyme of activity 100 kLU/g sold by NOVO Industries A/S under the tradename Lipolase Endolase Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO industries A/S PB4 Sodium perborate tetrahydrate of nominal formula NaBO₂.3H₂O.H₂O₂ PB1 Anhydrous sodium perborate bleach of nominal formula NaBO₂.H₂O₂ Percarbonate Sodium Percarbonate of nominal formula 2Na2CO3.3H2O2 NAC-OBS (Nonanamido caproyl) oxybenzene sulfonate in the form of the sodium salt. NOBS Nonanoyl oxybenzene sulfonate in the form of the sodium salt DPDA Diperoxydodecanedioic acid PAP N-phthaloylamidoperoxicaproic acid NAPAA Nonanoylamido peroxo-adipic acid NACA 6 nonylamino-6 oxo-capronic acid. TAED Tetracetylethylenediamine DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060 Photoactivated Sulfonated Zinc or aluminium Phthlocyanine encapsulated Brightener 1 Disodium 4,4′-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium 4,4′-bis(4-anilino-6-morpholino-1.3.5- triazin-2-yl)amino) stilbene-2:2′-disulfonate. HEDP 1,1-hydroxyethane diphosphonic acid PVNO Polyvinylpyridine N-oxide PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole QEA bis ((C₂H₅O)(C₂H₄O)_(n))(CH₃)— N⁺—C₆H₁₂—N⁺—(CH₃₎ bis ((C₂H₅O)—(C₂H₄O)_(n)), wherein n = from 20 to 30 SRP 1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone SRP 2 Diethoxylated poly (1,2 propylene terephtalate) short block polymer Silicone antifoam Polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.

In the following Examples all levels are quoted as parts per weight of the composition or % by weight of the composition, as indicated:

EXAMPLE 1

The following high density granular laundry detergent compositions A to F of particular utility under European machine wash conditions were prepared in accord with the invention:

A B C D E F LAS 2.0 2.0 1.5 3.0 5.0 4.0 TAS 5.0 0 2.0 0 0 2.0 C25E9 3.4 — — 3.4 5.4 2.4 C25E7 — 3.0 4.5 — — — C46AS 1.0 2.0 2.5 — 3.0 4.0 C24AS 3.0 2.0 5.0 7.0 1.0 0.5 SADS — — — — 1.0 — MBAS 16.5, 2.6 6.0 — 8.0 10.5 — 5.0 MBAS16,5, 1.5 — 7.0 — — 8.0 5.0 QAS II — — 0.8 — — 0.8 Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1 Carbonate 13.0 13.0 13.0 27.0 27.0 27.0 Citric acid 2.0 1.0 — — — — Silicate 1.4 1.4 1.4 3.0 3.0 3.0 Sulfate 26.1 26.1 26.1 26.1 26.1 26.1 MA/AA 0.3 0.3 0.3 0.3 0.3 0.3 CMC 0.2 0.2 0.2 0.2 0.2 0.2 PB4 9.0 9.0 9.0 — — — Percarbonate — — — 18.0 15.0 20.0 TAED — — 1.0 1.5 — — NAC-OBS 4.0 2.5 0.5 1.0 2.0 5.0 DTPMP 0.25 0.25 0.25 0.25 0.25 0.25 EDDS — — 0.25 0.4 — — HEDP 0.3 0.3 0.3 0.3 0.3 0.3 QBA 0.5 1.0 — — 0.5 — Protease 0.26 0.26 0.26 0.26 0.26 0.26 Amylase 0.1 0.1 0.1 0.1 0.1 0.1 Photoactivated 15 ppm 15 ppm 15 ppm 15 ppm 15 ppm 15 ppm bleach (ppm) Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09 Perfume 0.3 0.3 0.3 0.3 0.3 0.3 Silicone antifoam 0.5 0.5 0.5 0.5 0.5 0.5 Density in g/litre 850 850 850 850 850 850

EXAMPLE 2

The following granular laundry detergent compositions G to I of bulk density 750 g/liter are compositions according to the invention:

G H I LAS 2.0 2.5 1.5 TAS 1.25 2.86 1.57 C45AS 3.5 3.24 2.0 C25AE3S — 0.76 1.0 C45E7 3.25 — — C25E3 — 3.5 — QAS I 0.8 2.0 — MBAS 17, 1.7 7.0 — 5.0 DBAS 17, 2.3 — 11.0 — STPP 19.7 — — Zeolite A — 19.5 19.5 NaSKS-6/silicate (79:21) — 10.6 10.6 Citric acid/citrate 2.0 4.0 1.0 Carbonate 6.1 21.4 21.4 Bicarbonate — 2.0 2.0 Silicate 6.8 — — Sodium sulfate 39.8 — 7.0 PB4 5.0 12.7 — TAED 0.5 0.2 — NAC OBS 1.0 2.2 — DTPMP 0.25 0.2 0.2 HEDP — 0.3 0.3 Protease 0.26 0.85 0.85 Lipase 0.15 0.15 0.15 Cellulase 0.28 0.28 0.28 Amylase 0.1 0.1 0.1 MA/AA 0.8 1.6 1.6 CMC 0.2 0.4 0.4 PVP — — 0.8 Photoactivated bleach (ppm) 15 ppm 27 ppm 27 ppm Brightener 1 0.08 0.19 0.19 Brightener 2 — 0.04 0.04 Perfume 0.3 0.3 0.3 Silicone antifoam 0.5 2.4 2.4 Minors/misc to 100% n.a. n.a.

EXAMPLE 3

The following are detergent formulations, according to the present invention where J is a phosphorus-containing detergent composition, K is a zeolite-containing detergent composition and L is a compact detergent composition:

J K L M Blown Powder STPP 24.0 — 24.0 — Zeolite A — 24.0 — 24.0 C45AS 4.0 — 4.0 5.0 QAS I — 1.0 — — MBAS 17, 1.5 4.0 — 10.0 6.0 MBAS 17, 2.1 2.0 11.0 — — SASDE2S 2.0 — — — C₂₅ AE₃S — 1.0 — 1.0 MA/AA 2.0 4.0 2.0 4.0 LAS 4.0 2.0 3.0 1.6 TAS — 4.0 2.0 — Silicate 7.0 3.0 3.0 3.0 CMC 1.0 1.0 0.5 1.0 Brightener 2 0.2 0.2 0.2 0.2 Soap 1.0 — — 1.0 DTPMP 0.4 0.4 0.2 0.4 Spray On C45E7 — 2.5 — — C25E3 2.5 — — 1.5 Silicone antifoam 0.3 0.3 0.3 0.3 Perfume 0.3 0.3 0.3 0.3 Dry additives QEA — 0.5 1.0 — Carbonate 6.0 13.0 15.0 13.0 PB4 18.0 18.0 10.0 — PB1 4.0 4.0 — — NOBS 3.0 4.2 1.0 — Photoactivated bleach 0.02 0.02 0.02 0.02 Manganese catalyst — — 0.5 — Protease 1.0 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 0.4 Amylase 0.25 0.30 0.15 0.3 Dry mixed sodium sulfate 3.0 3.0 5.0 3.0 Balance (Moisture & 100.0 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 630 670 670 670

EXAMPLE 4

The following are detergent formulations according to the present invention:

N O P Q LAS — 4.0 3.0 2.0 TAS — 1.0 4.0 — MBAS 17, 1.9 5.0 10.0 16.0 8.0 C45AS 4.0 4.0 6.0 6.0 MES 3.0 — — — QAS II 0.4 — 1.0 — TFAA — 1.0 — — C25E5/C45E7/C₂₅E₃ — 2.0 — 1.0 STPP 30.0 18.0 30.0 22.0 Silicate 9.0 5.0 10.0 8.0 Carbonate 13.0 7.5 — 5.0 Bicarbonate — 7.5 — — DTPMP 0.7 1.0 — — SRP 1 0.3 0.2 — 0.1 MA/AA 2.0 1.5 2.0 1.0 CMC 0.8 0.4 0.4 0.2 Protease 0.8 1.0 0.5 0.5 Amylase 0.8 0.4 — 0.25 Lipase 0.2 0.1 0.2 0.1 Cellulase 0.15 0.05 — — Photoactivated 70 ppm 45 ppm — 10 ppm bleach (ppm) Brightener 1 0.2 0.2 0.08 0.2 PB1 6.0 2.0 — — NACA — — — 3.0 NAC OBS 2.0 1.0 0.9 3.1 Balance (Moisture 100 100 100 100 and Miscellaneous)

EXAMPLE 5

The following are detergent formulations according to the present invention:

R S T Blown Powder MBAS 16.5, 1.5 — 10.0 — MBAS 17, 3.0 6.0 — MBAS 17.5, 1.8 — — 12.0 Zeolite A 30.0 22.0 6.0 Sodium sulfate 19.0 5.0 7.0 MA/AA 3.0 3.0 6.0 MES — 5.0 — LAS 3.0 — 3.5 C45A5 3.0 4.0 7.0 Silicate — 1.0 5.0 Soap — — 2.0 Brightener 1 0.2 0.2 0.2 Carbonate 8.0 16.0 20.0 Spray On C45E5 1.0 1.0 — Dry additives PVPVI/PVNO 0.5 0.5 0.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 Cellulase 0.1 0.1 0.1 NOBS — 6.1 — NAC OBS — — 4.5 Sodium sulfate — 6.0 — Balance Moisture and 100 100 100 Miscellaneous)

EXAMPLE 6

The following are high density and bleach-containing detergent formulations according to the present invention:

U V W Blown Powder Zeolite A 15.0 15.0 15.0 Sodium sulfate 0.0 5.0 0.0 LAS 3.0 — 3.0 C45AS 3.0 2.0 4.0 QAS — — 1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Agglomerates LAS — 1.0 1.0 MBAS16.5, 1.8 12 8.0 14.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray On Encapsulated Perfume 0.3 0.3 0.3 C25E3 2.0 — 2.0 Dry additives QEA — — 0.5 Citrate 5.0 — 2.0 Bicarbonate — 3.0 — Carbonate 8.0 15.0 10.0 NAC OBS 6.0 — 5.0 Manganese catalyst — — 0.3 NOBS — 2.0 — PB1 14.0 7.0 10.0 Polyethylene oxide of MW 5,000,000 — — 0.2 Bentonite clay — — 10.0 Citric acid — — 0.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 Balance Moisture and 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 850 850 850

EXAMPLE 7

The following are high density detergent formulations according to the present invention:

X Y Agglomerate MES — 2.0 LAS 2.0 — TAS — 2.0 C4SAS 6.0 4.0 MBAS16.5, 1.9 4.0 9.0 MBAS16.5, 3.5 4.0 — Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA/AA 4.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0.4 Spray On C25E3 1.0 1.0 Perfume 0.5 0.5 Dry Adds HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate — 1.0 Citric acid 2.0 — NAC OBS 4.1 — TAED 0.8 2.0 Percarbonate 20.0 20.0 SRP 1 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0.4 Cellulase 0.6 0.6 Amylase 0.6 0.6 QEA 1.0 — Silicone antifoam 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 — Density (g/litre) 850 850

EXAMPLE 8

The following granular detergent formulations are examples of the present invention.

AH AI AJ Blown powder MES — 2.0 — LAS 2.0 — 3.0 C45AS — 1.0 — C46AS 4.0 — — C45AE35 2.0 5.0 3.0 MBAS18, 4.0 8.0 — — Zeolite A 16.0 19.0 16.0 MA/AA 3.0 — — AA 3.0 2.0 3.0 Sodium sulfate 3.3 24.0 13.3 Silicate 1.0 2.0 1.0 Carbonate 9.0 25.7 8.0 QEA 0.4 — 0.5 PBG 4000 — 1.0 1.5 Brightener 0.3 0.3 0.3 Spray on C25E5 0.5 1.0 — Perfume 0.3 1.0 0.3 Agglomerates C45AS 5.0 2.0 5.0 LAS 1.0 1.0 2.0 MBAS17, 1.7 — 8.0 14 Zeolite A 7.5 — 7.5 HEDP 1.0 — 2.0 Carbonate 4.0 — 4.0 PEG 4000 0.5 — 0.5 Misc(water etc) 2.0 — 2.0 Dry additives NOBS 4.0 — — TAED — — 2.0 PB4 1.0 — 2.0 Carbonate 5.3 — 2.5 Cumeme sulfonic acid 2.0 — 2.0 Lipase 0.4 0.1 0.05 Cellulase 0.2 — 0.2 Amylase 0.3 — — Protease 1.6 — 1.6 PVPVI 0.5 — — PVNO 0.5 — — SRP1 0.5 — — Silicone antifoam 0.2 — 0.2

EXAMPLE 9

AK AL AM AN AO AP C45AS 11.0 5.0 4.6 6.5 4.1 9.0 C2SAES 1.3 1.0 — 1.3 1.0 — LAS 9.4 6.6 2.7 3.0 2.0 4.2 C25E3/C25E5 1.5 4.7 3.3 1.5 4.7 3.3 MBAS 16.5, 1.7 15.0 12.0 10.0 10.2 7.0 14.1 QAS — 1.15 0.6 — 1.7 — Zeolite A 27.0 16.7 11.2 27.0 16.7 11.2 SKS-6 — 9.0 7.5 — 9.0 7.5 Citric acid — 1.5 — — 1.5 — MA/AA — 0.6 — — 0.6 — MA/AA 3 — — 7.03 — — 7.03 AA 2.3 — — 2.8 — — EDDS — 0.3 — — 0.3 — HEDP — 0.5 — — 0.5 — Carbonate 26.0 12.5 14.5 26.0 12.5 14.0 Silicate 0.58 0.8 12 0.58 0.8 12 PB1 1.0 — 4.0 1.0 — 4.0 NACA-OBS — 2.7 — — 2.7 — PC — 17.3 — — 17.3 — NOBS — 2.7 4.0 — — 4.0 TAED — 3.5 — — 3.5 — Protease 0.25 0.36 0.2 0.26 0.36 0.2 Lipase — — — — — — Cellulase 0.3 0.26 — 0.3 0.26 — Amylase — 0.36 — — 0.36 — Brightener 0.17 0.06 0.30 0.17 0.06 0.30 SRP1 0.4 0.2 0.5 0.4 0.2 0.5 PEG 1.6 — 0.19 1.6 — 0.19 Sulfate 5.5 6.4 3.5 5.5 6.4 3.5 CMC — 0.5 — — 0.5 — MgSO4 — 0.13 — — 0.13 — Photobleach — 0.0026 — — 0.0026 — Silicone anti-foam 0.02 0.21 0.17 0.02 0.21 0.17 Perfume 0.42 0.55 0.25 0.42 0.55 0.25

EXAMPLE 10

The following laundry detergent compositions AQ to AT are prepared in accord with the invention:

AQ AR AS AT MBAS 16.5, 1.7 22 16.5 11 5.5 C45 AS 9.0 8.0 4.1 4 C45E1S 1.0 — — — LAS 5.0 6.0 3.7 — C16 SAS — 2.0 — — MES — — — 4 C23E6.5 0.5 1.5 — 1.5 Zeolite A 27.8 27.8 27.8 27.8 AA 2.3 2.3 2.3 2.3 Carbonate 27.3 27.3 27.3 27.3 Silicate 0.6 0.6 0.6 0.6 Perborate 1.0 1.0 1.0 1.0 Protease 0.3 0.3 0.3 0.3 Cellulase 0.3 0.3 0.3 0.3 SRP1 0.4 0.4 0.4 0.4 Brightener 0.2 0.2 0.2 0.2 PEG 1.6 1.6 1.6 1.6 Sulfate 5.5 5.5 5.5 5.5 Silicone Antifoam 0.42 0.42 0.42 0.42 Moisture & Minors Balance Density (g/L) 663 663 663 663

EXAMPLE 11

The following laundry detergent compositions AU to AY are prepared in accord with the invention:

AU AV AW AX AY MBAS 16.5, 1.7 14.8 16.4 12.3 8.2 4.1 C45 AS 6.0 8.0 4.3 4.0 5.0 C45E3S 2.0 — — 1.0 — LAS 5.0 — 3.7 3.0 5.0 C16 SAS — 1.0 — — — MES — 5.0 — — — TFAA 1.6 0 0 0 0 C24E3 4.9 4.9 4.9 4.9 4.9 Zeolite A 15 15 15 15 15 NaSKS-6 11 11 11 11 11 Citrate/citric 1.0 3 3 2.0 — MA/AA 4.8 4.8 4.8 4.8 4.8 HEDP 0.5 0.5 0.5 0.5 0.5 Carbonate 3.5 8.5 8.5 8.5 8.5 Percarbonate 20.7 20.7 20.7 20.7 20.7 TAED 4.8 4.8 — — 4.8 NACA-OBS — — 5.0 6.0 2.0 Protease 0.9 0.9 0.9 0.9 0.9 Lipase 0.15 0.15 0.15 0.15 0.15 Cellulase 0.26 0.26 0.26 0.26 0.26 Amylase 0.36 0.36 0.36 0.36 0.36 SRP1 0.2 0.2 0.2 0.2 0.2 Brightener 0.2 0.2 0.2 0.2 0.2 Sulfate 2.3 2.3 2.3 2.3 2.3 QEA 1.0 1.0 — — — QAS 1.0 — — — 1.0 Silicone Antifoam 0.4 0.4 0.4 0.4 0.4 Moisture & Minors Balance Density (g/L) 850 850 850 850

EXAMPLE 12

The following laundry detergent compositions AZ to Ee are prepared in accord with the invention:

AZ Aa Bb Cc Dd Ee MBAS 16.5, 1.7 32 24 12 16 16 8 C45 AS 7.8 8 4.5 5.0 2.0 4.0 C45E1S 5 — — 2.0 2.0 2.0 LAS 5 6 3.8 4.0 8.8 — C16 SAS — — — — 2.0 — MES — — — — — 5.0 C23E6.5 3.6 3.6 3.6 3.6 3.6 3.6 QAS — 0.5 — — 0.5 — Zeolite A 9.0 9.0 9.0 9.0 9.0 9.0 Polycarboxylate 7.0 7.0 7.0 7.0 7.0 7.0 Carbonate 18.4 18.4 18.4 18.4 18.4 18.4 Silicate 11.3 11.3 11.3 11.3 11.3 11.3 Perborate 3.9 3.9 3.9 3.9 3.9 3.9 NOBS 4.1 4.1 4.1 4.1 4.1 4.1 Protease 0.9 0.9 0.9 0.9 0.9 0.9 SRP 0.5 0.5 0.5 0.5 0.5 0.5 Brightener 0.3 0.3 0.3 0.3 0.3 0.3 PEG 0.2 0.2 0.2 0.2 0.2 0.2 Sulfate 5.1 5.1 5.1 5.1 5.1 5.1 Silicone Antifoam 0.2 0.2 0.2 0.2 0.2 0.2 Moisture & Minors Balance Density(g/L) 810 810 810 810 810 810 

What is claimed is:
 1. A detergent composition comprising a) at least 0.5% by weight of the composition of a surfactant system, comprising longer alkyl chain, mid-chain branched surfactant compounds of the formula: A^(b)—X—B  wherein: (I) A^(b) is a hydrophobic mid-chain branched alkyl moiety, having in total 9 to 22 carbons in the moiety having: (1) a longest linear carbon chain attached to the —X—B moiety in the range of from 8 to 21 carbon atoms; (2) one or more C₁-C₃ alkyl moieties branching from this longest linear carbon chain; (3) at least one of the branching alkyl moieties is attached directly to a carbon of the longest linear carbon chain at a position within the range of the position 2 carbon, counting from position 1 carbon (#1) which is attached to the —X—B moiety, to the position of the terminal carbon minus 2 carbons, (the (ω-2) carbon); and (4) when more than one of these compounds is present, the average total number of carbon atoms in the A^(b)—X moieties in the above formula is within the range of greater than 14.5 to about 18; (II) B is a hydrophobic moiety selected from sulfates, sulfonates, amine oxides, polyoxyalkylene, alkoxylated sulfates, polyhydroxy moieties, phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccaminates, polyalkoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulfates, polyglycerol ethers, polyglycerol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonioalkanesulfonates, amidopropyl betaines, alkylated quats, alkyated/polyhydroxyalkylated quats, alkylated quats, alkylated/polyhydroxylated oxypropyl quats, imidazolines, 2-yl-succinates, sulfonated alkyl esters, and sulfonated fatty acids; and (III) X is selected from —CH₂— and —C(O)—; and b) at least 0.5% by weight of the composition of an additional sulfate surfactant; and c) at least 0.5% by weight of the composition of an additional sulfonate surfactant, whereby the ratio of the surfactant system a) to the surfactant b) is from 20:1 to 1:20 and the ratio of surfactant system a) to the surfactant c) is from 20:1 to 1:10.
 2. A detergent composition according to claim 1 wherein the surfactant compounds of the surfactant system a) are of the above formula wherein the A^(b) moiety is a branched primary all moiety having the formula:

wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula, including the R, R¹, and R³ branching, is from 13 to 19; R, R¹, and R² are each independently selected from hydrogen and C₁-C₃ alkyl provided R, R¹, and R² are not all hydrogen and, when z is 0, at least R or R¹ is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer from 0 to 13; and w+x+y+z is from 7 to
 13. 3. A detergent composition according to claim 1 wherein the surfactant system a) comprises at least 20% by weight of one or more mid-chain branched alkyl sulfates having the formula:

or mixtures thereof; wherein M represents one or more cations; a, b, d, and e are integers, a+b is from 10 to 16, d+e is from 8 to 14 and wherein further when a+b=10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a+b=11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a+b=12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a+b=13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a+b=14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a+b=15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a+b=16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d+e=8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d+e=9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d+e=10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d+e=11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d+e=12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d+e=13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d+e=14, d is an integer from 2 to 13 and e is an integer from 1 to 12; whereby the average total number of carbon atoms in the branched primary alkyl moieties is from 14.5 to 17.5.
 4. A detergent composition according to claim 3 wherein the average total number of carbon atoms in the branched primary alkyl moieties is from 16 to 17, and the sulfate surfactant is of formula (I).
 5. A detergent composition according to claim 1 wherein the surfactant b) is a C₁₀₋₁₈ alkyl sulfate surfactant.
 6. A detergent composition according to claim 1 wherein the surfactant c) is a linear C₁₂₋₁₆ alkyl benzene sulfonate or a x.
 7. A detergent composition according to claim 1 wherein the ratio of surfactant system a) to surfactant b) is from 4:1 to 1:2 and of surfactant system a) to surfactant c) is from 5:1 to 1:1.
 8. A detergent composition according to claim 1 wherein a nonionic surfactant is present at a ratio to the anionic surfactant system a) of from 5:1 to 1:10.
 9. A detergent composition according to claim 7 wherein the nonionic surfactant is present at a level of from 0.5% to 20% by weight of the detergent composition.
 10. A detergent composition according to claim 1 in the form of a solid laundry detergent composition. 